WO2012090406A1 - 液晶性ポリエステルおよびその製造方法 - Google Patents
液晶性ポリエステルおよびその製造方法 Download PDFInfo
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- WO2012090406A1 WO2012090406A1 PCT/JP2011/006969 JP2011006969W WO2012090406A1 WO 2012090406 A1 WO2012090406 A1 WO 2012090406A1 JP 2011006969 W JP2011006969 W JP 2011006969W WO 2012090406 A1 WO2012090406 A1 WO 2012090406A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
Definitions
- the present invention relates to a liquid crystalline polyester excellent in precision molding stability represented by variations in resin metering time and injection peak pressure during injection molding, dimensional stability during reflow, and strength of a small thin molded article, and a method for producing the same
- the present invention relates to a resin composition and a molded product obtained therefrom.
- Liquid crystalline polyester can improve its heat resistance, fluidity, dimensional stability, electrical properties, etc. by controlling its crystallinity according to its molecular structure and manufacturing method, etc. Demand is growing mainly for precision molded products.
- the liquid crystalline polyester has high temperature sensitivity at the time of melting, the following problems may occur.
- the resin metering time and injection peak pressure vary during injection molding, resulting in decreased productivity, the strength of small thin molded products represented by the winding strength of insulators, the polymer itself and the residual during molding. Problems such as large changes in dimensions before and after heating due to stress may occur.
- a problem that occurs in the liquid crystalline resin is to control the molecular chain of the liquid crystalline resin by controlling ⁇ S (melting entropy), which is an index indicating the crystallinity of the liquid crystalline resin, to be low.
- ⁇ S melting entropy
- Studies have been made to arrange in an ordered state see, for example, Patent Documents 1 and 2).
- studies have been made to improve the abrasion resistance of fibers made of a liquid crystalline resin by reducing ⁇ H (heat of fusion) (see, for example, Patent Document 4).
- the present invention is a liquid crystalline polyester excellent in precision molding stability represented by variations in resin measurement time and injection peak pressure during injection molding, dimensional stability during reflow, and strength of a small thin molded article,
- An object of the present invention is to provide a production method, a resin composition obtained therefrom, and a molded product.
- a liquid crystalline polyester having a specific composition and having a specific range of ⁇ S (melting entropy) specifically has a resin metering time and an injection peak at the time of injection molding.
- the inventors have found that the pressure variation is small, the precision molding stability is excellent, the dimensional stability at the time of reflow is high, and the strength of a small thin-walled molded article is high.
- the present invention has been made to solve at least a part of the above-described problems, and embodiments of the present invention can include at least a part of the following configurations.
- a liquid crystalline polyester composed of the following structural units (I), (II), (III), (IV) and (V).
- the structural unit (I) is 68 to 80 mol% with respect to the total of the structural units (I), (II) and (III).
- the structural unit (II) is 55 to 75 mol% with respect to the total of the structural units (II) and (III).
- the structural unit (IV) is 60 to 85 mol% with respect to the total of the structural units (IV) and (V).
- the sum of the structural units (II) and (III) and the sum of (IV) and (V) are substantially equimolar.
- ⁇ S melting entropy
- ⁇ S (melting entropy) 1.0 to 3.0 ⁇ 10 ⁇ 3 J / g ⁇ K.
- ⁇ S (J / g ⁇ K) ⁇ Hm (J / g) / Tm (K) [1]
- Tm is a differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer which has been polymerized is measured at room temperature to 20 ° C./minute, the temperature is maintained at Tm1 + 20 ° C. for 5 minutes.
- the temperature After cooling to 20 ° C./min, the temperature is once cooled down to room temperature, and after measuring the endothermic peak temperature (Tm2) observed when the temperature is again measured at 20 ° C./min, the temperature is 5 at Tm1 + 20 ° C. After holding for a minute, the temperature is once cooled to room temperature under a temperature drop condition of 20 ° C./min, and again indicates an endothermic peak temperature (Tm3) observed when measured under a temperature rise condition of 20 ° C./min. ⁇ Hm is the Tm3 Endothermic peak area ( ⁇ Hm3).)
- the dispersity (Mw / Mn) may exceed 2.5.
- the average temperature rising rate may be less than 1.0 ° C./min.
- the said average temperature increase rate is good also as exceeding 1.6 degreeC / min.
- a liquid crystalline polyester resin composition comprising 10 to 200 parts by weight of a filler per 100 parts by weight of the liquid crystalline polyester described in (1) or (2).
- the content of the filler with respect to the liquid crystalline polyester described in the above (1) or (2) may be less than 10 parts by weight with respect to 100 parts by weight of the liquid crystalline polyester. Moreover, content of the filler with respect to liquid crystalline polyester as described in said (1) or (2) is good also as exceeding 200 weight part with respect to 100 weight part of liquid crystalline polyester.
- a molded product produced by a method different from melt molding using the liquid crystalline polyester described in (1) or (2) or the liquid crystalline polyester resin composition described in (4) may be used.
- the liquid crystal has high precision molding stability represented by variations in resin metering time and injection peak pressure at the time of injection molding, and has excellent dimensional stability at the time of reflow and strength of a small thin-walled molded product. Can be obtained. Further, by using the liquid crystalline polyester of the embodiment of the present invention, a molded product excellent in dimensional stability during reflow and strength of a small thin molded product can be provided.
- the liquid crystalline polyester as an embodiment of the present invention is a polyester called a thermotropic liquid crystal polymer that exhibits optical anisotropy when melted, and includes the following structural units (I), (II), (III), (IV) and (V), the structural unit (I) is 68 to 80 mol% based on the total of the structural units (I), (II) and (III), and the structural unit (II) is the structural unit (II).
- Tm1 endothermic peak temperature
- Tm2 endothermic peak temperature
- Tm3 endothermic peak area
- the structural unit (I) is a structural unit generated from p-hydroxybenzoic acid
- the structural unit (II) is a structural unit generated from 4,4′-dihydroxybiphenyl
- the structural unit (III) is a structure generated from hydroquinone.
- the structural unit (IV) represents a structural unit generated from terephthalic acid
- the structural unit (V) represents a structural unit generated from isophthalic acid.
- the structural unit (I) is 68 to 80 mol% with respect to the total of the structural units (I), (II) and (III). 70 mol% or more is preferable and 73 mol% or more is more preferable. On the other hand, 78 mol% or less is preferable.
- the structural unit (II) is 55 to 75 mol% with respect to the total of the structural units (II) and (III). 58 mol% or more is preferable. On the other hand, 70 mol% or less is preferable, and 65 mol% or less is more preferable.
- the structural unit (IV) is 60 to 85 mol% with respect to the total of the structural units (IV) and (V). 65 mol% or more is preferable and 70 mol% or more is more preferable.
- the sum of the structural units (II) and (III) and the sum of (IV) and (V) are substantially equimolar.
- substantially equimolar means that the structural unit constituting the polymer main chain excluding the terminal is equimolar. For this reason, the aspect which does not necessarily become equimolar when it includes even the structural unit which comprises the terminal can satisfy the requirement of “substantially equimolar”.
- the content of each structural unit is determined by weighing the liquid crystalline polyester in an NMR (nuclear magnetic resonance) test tube and dissolving the liquid crystalline polyester in a solvent (for example, pentafluorophenol / heavy tetrachloroethane- d 2 mixed solvent), and 1 H-NMR spectrum measurement can be performed and calculated from the peak area ratio derived from each structural unit.
- a solvent for example, pentafluorophenol / heavy tetrachloroethane- d 2 mixed solvent
- the liquid crystalline polyester of the embodiment of the present invention is characterized in that ⁇ S (melting entropy) defined by the following formula [1] is 1.0 to 3.0 ⁇ 10 ⁇ 3 J / g ⁇ K. To do.
- ⁇ S (J / g ⁇ K) ⁇ Hm (J / g) / Tm (K) [1]
- Tm (melting point) is a differential calorimetry.
- Tm1 + 20 ° C. After observing the endothermic peak temperature (Tm1) observed when the polymer which has been polymerized is measured from room temperature under a temperature rising condition of 20 ° C./min, Tm1 + 20 ° C. After maintaining at a temperature for 5 minutes, the sample is once cooled to room temperature under a temperature drop condition of 20 ° C./min, and after observation of an endothermic peak temperature (Tm2) observed at a temperature rise condition of 20 ° C./min, Tm1 + 20 After holding at a temperature of 5 ° C.
- Tm1 + 20 After observing the endothermic peak temperature (Tm1) observed when the polymer which has been polymerized is measured from room temperature under a temperature rising condition of 20 ° C./min, Tm1 + 20 ° C. After maintaining at a temperature for 5 minutes, the sample is once cooled to room temperature under a temperature drop condition of 20 ° C./min, and after observation of an endothermic peak temperature (Tm2) observed at
- Tm3 endothermic peak temperature
- ⁇ Hm endothermic peak area
- Tm2 and Tm3, and their endothermic peak areas are equivalent, but if polymerized and then stretched after melting when processed into fibers or films, it is not necessarily equivalent. It may not be possible.
- the polymer molecules are strongly oriented, and the orientation is not sufficiently relaxed even at the second temperature increase in differential calorimetry, and Tm2 and ⁇ Hm2 do not show the properties of the original polymer. This is because Tm3 and ⁇ Hm2 and ⁇ Hm3 may change. Therefore, when calculating the accurate ⁇ S (melting entropy) of the polymer, it is necessary to calculate it using Tm3 and ⁇ Hm3 which have no external factors.
- the liquid crystalline polyester of the embodiment of the present invention is characterized in that ⁇ S (melting entropy) is 1.0 to 3.0 ⁇ 10 ⁇ 3 J / g ⁇ K. Preferably it is 1.2 ⁇ 10 ⁇ 3 J / g ⁇ K or more, more preferably 1.5 ⁇ 10 ⁇ 3 J / g ⁇ K or more. Moreover, 2.6 * 10 ⁇ -3 > J / g * K or less is preferable and 2.2 * 10 ⁇ -3 > J / g * K or less is more preferable.
- ⁇ S melting entropy
- dispersion in melting occurs during injection molding measurement, so dispersion in resin measurement time and injection peak pressure increases, and precision molding stability Decreases.
- the crystallinity is low, distortion is likely to occur in the molecule due to molding, the amount of warpage after reflow treatment of the molded product increases, and the dimensional stability during reflow decreases.
- the surface hardness is lowered due to the decrease in crystallinity, the strength is reduced when the molded product is a small thin molded product.
- the melting point (Tm) of the liquid crystalline polyester of the embodiment of the present invention is preferably 220 to 350 ° C., more preferably 270 to 345 ° C., and further preferably 300 to 340 from the viewpoint of the balance between processability and heat resistance. ° C.
- the number average molecular weight of the liquid crystalline polyester of the embodiment of the present invention is preferably 3,000 to 50,000, more preferably 8,000 to 30,000, still more preferably 8,000 to 20,000. .
- the liquid crystalline polyester of the embodiment of the present invention preferably has a dispersity of 2.5 or less, which is a value obtained by dividing the weight average molecular weight by the number average molecular weight.
- the degree of dispersion is 2.5 or less, the molecular weight distribution is sharp, so that the meltability and crystallinity are good.
- the precision molding stability and the strength of small thin molded products are further improved.
- the improvement in the strength of the small thin molded product by setting the degree of dispersion to 2.5 or less is presumed to be because the surface hardness of the molded product increases due to high crystallization.
- the degree of dispersion is preferably 2.2 or less, more preferably 2.0 or less.
- the weight average molecular weight and the number average molecular weight can be measured by GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the liquid crystalline polyester is soluble as an eluent.
- the solvent in which the liquid crystalline polyester is soluble include halogenated phenols and a mixed solvent of a halogenated phenol and a general organic solvent.
- pentafluorophenol and a mixed solvent of pentafluorophenol and chloroform is preferable from the viewpoint of handleability.
- the melt viscosity of the liquid crystalline polyester of the embodiment of the present invention is preferably 1 to 200 Pa ⁇ s, more preferably 10 to 100 Pa ⁇ s, and further preferably 20 to 50 Pa ⁇ s.
- the melt viscosity is a value measured with a Koka flow tester under the condition of melting point of liquid crystalline polyester + 10 ° C. and shear rate of 1,000 / sec.
- the liquid crystalline polyester of the embodiment of the present invention can be obtained by a known deacetic acid polymerization method of polyester. For example, after the acetylation of a predetermined amount of the aromatic hydroxycarboxylic acid and the phenolic hydroxyl group of the aromatic diol using acetic anhydride, a method of deacetic acid polymerization may be mentioned.
- the aromatic hydroxycarboxylic acid and the aromatic diol are p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and hydroquinone.
- acetylation step for example, a predetermined amount of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, and acetic anhydride are charged into a reaction vessel, and the reaction is performed in a nitrogen gas atmosphere. It is preferable to acetylate the hydroxyl group by heating with stirring.
- the reaction vessel may be provided with a stirring blade, may be provided with a distillation pipe, and may be provided with a discharge port in the lower part.
- the conditions for acetylation are usually in the range of 130 to 150 ° C. for 1 to 3 hours.
- the amount of acetic anhydride used is preferably 1.00 to 1.15 molar equivalent of the total of the phenolic hydroxyl groups of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and hydroquinone, and 1.05 to 1. 12 molar equivalents are more preferred, and 1.07 to 1.12 molar equivalents are even more preferred.
- a melt polymerization method in which the reaction is performed under reduced pressure at a temperature at which the liquid crystalline polyester melts to complete the polymerization reaction is preferable. More specifically, after the acetylation, it is preferable to carry out the deacetic acid polymerization by increasing the temperature above the melting temperature of the liquid crystalline polyester and allowing the reaction to proceed while distilling off acetic acid.
- the melt polymerization method is an advantageous method for producing a uniform polymer, and is preferable because an excellent liquid crystalline polyester with less gas generation and a resin composition thereof can be obtained.
- the temperature for the deacetic acid polymerization is a general melting temperature of the liquid crystalline polyester, for example, in the range of 250 to 365 ° C., and preferably a melting point of the liquid crystalline polyester + 10 ° C. or higher.
- the degree of vacuum during the polymerization is usually 0.1 mmHg (13.3 Pa) to 20 mmHg (2660 Pa), preferably 10 mmHg (1330 Pa) or less, more preferably 5 mmHg (665 Pa) or less.
- acetylation and polymerization may be performed continuously in the same reaction vessel or in different reaction vessels.
- the polymerization in order to easily control ⁇ S (melting entropy) of the liquid crystalline polyester within the desired range, the polymerization can jacket temperature in the step of deacetic acid polymerization is changed from 270 ° C. to the maximum polymerization temperature. It is preferable to raise the temperature so that the average rate of temperature rise is 1.0 to 1.6 ° C./min. Since the oligomerization reaction of the acetylated monomer can be controlled by setting the average temperature rising rate from 270 ° C.
- the average rate of temperature rise is preferably 1.2 ° C./min or more, and more preferably 1.4 ° C./min or more.
- the average rate of temperature increase is preferably 1.2 ° C./min or more, and more preferably 1.4 ° C./min or more.
- the reactivity of p-hydroxybenzoic acid can be moderately suppressed and blocking can be moderately suppressed. . Therefore, a liquid crystalline polyester having ⁇ S (melting entropy) of 3.0 ⁇ 10 ⁇ 3 J / g ⁇ K or less can be easily obtained.
- the internal temperature easily follows the polymerization can jacket temperature rise, and the productivity is improved.
- the average temperature increase rate of the polymerization can jacket since the oligomerization reaction of the acetylated monomer starts to proceed from around 270 ° C., the average temperature increase rate from the polymerization can jacket temperature of 270 ° C. to the maximum polymerization temperature is reached. Pay attention.
- the obtained polymer is taken out from the reaction vessel by pressurizing the inside of the reaction vessel at a temperature at which the polymer melts, discharging the polymer from the discharge port provided in the reaction vessel, and cooling the discharged polymer.
- the method of cooling in water can be mentioned.
- the pressurization in the reaction vessel may be 0.02 to 0.5 MPa, for example.
- the discharge port may be provided at the lower part of the reaction vessel. Moreover, what is necessary is just to discharge a polymer in a strand form from a discharge outlet. Resin pellets can be obtained by cutting the polymer cooled in the cooling liquid into pellets.
- the polymerization reaction can be completed by a solid phase polymerization method.
- the liquid crystalline polyester polymer or oligomer of the embodiment of the present invention is pulverized with a pulverizer, heated in a nitrogen stream or under reduced pressure, polymerized to a desired degree of polymerization, and the reaction is completed. .
- the heating may be performed for 1 to 50 hours within the range of the melting point of the liquid crystalline polyester of ⁇ 5 ° C. to the melting point of ⁇ 50 ° C. (eg, 200 to 300 ° C.).
- the polymerization reaction of the liquid crystalline polyester proceeds even without catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metal magnesium can also be used as a catalyst.
- metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metal magnesium can also be used as a catalyst.
- a resin composition can be obtained by adding a filler to the liquid crystalline polyester of the embodiment of the present invention within a range not impairing the effects of the present invention.
- the inclusion of the filler is preferable because the effect of the present invention appears remarkably due to the reinforcing effect of the filler.
- the filler include fillers such as a fiber, a plate, a powder, and a granule.
- whisker-like filler mica, talc, kaolin, silica, glass beads, glass flakes, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate and graphite, etc.
- the filler used in the embodiment of the present invention has its surface treated with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) and other surface treatment agents. Also good.
- glass fiber is particularly preferable, and the winding strength can be further improved.
- the type of glass fiber is not particularly limited as long as it is generally used for reinforcing resin, and can be selected from, for example, long fiber type or short fiber type chopped strands and milled fibers.
- the glass fiber used in the embodiment of the present invention is preferably weakly alkaline in terms of mechanical strength.
- glass fibers having a silicon oxide content of 50 to 80% by weight are preferably used, and more preferably glass fibers having a silicon oxide content of 65 to 77% by weight.
- the glass fiber is preferably treated with an epoxy-based, urethane-based, acrylic-based coating or sizing agent, and epoxy-based is particularly preferable.
- the glass fiber may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as epoxy resin. Two or more fillers may be used in combination.
- the content of the filler is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, and more preferably 30 parts by weight or more with respect to 100 parts by weight of the liquid crystalline polyester. Moreover, 200 weight part or less is preferable, 150 weight part or less is more preferable, and 100 weight part or less is more preferable.
- the liquid crystalline polyester resin composition of the embodiment of the present invention further includes an antioxidant, a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites, and substituted products thereof as long as the effects of the present invention are not impaired. ), Ultraviolet absorbers (eg, resorcinol, salicylate), anti-coloring agents such as phosphites and hypophosphites, lubricants, mold release agents (montanic acid and metal salts thereof, esters thereof, half esters thereof, Stearyl alcohol, stearamide and polyethylene wax), colorants including dyes or pigments, carbon black as a conductive agent or colorant, crystal nucleating agent, plasticizer, flame retardant (bromine flame retardant, phosphorus flame retardant, red phosphorus , Silicone flame retardants, etc.), flame retardant aids, and conventional additives selected from antistatic agents Kill. Or you may mix
- the method of blending fillers, additives and the like with the liquid crystalline polyester of the embodiment of the present invention is not particularly limited, and includes dry blending and solution blending, addition of liquid crystalline polyester during polymerization, melt kneading, and the like.
- melt kneading is preferable.
- a known method can be used for melt kneading.
- a Banbury mixer, a rubber roll machine, a kneader, a single screw or twin screw extruder can be used, and it is preferable to use a twin screw extruder.
- the melt kneading temperature is preferably not less than the melting point of the liquid crystalline polyester and not more than the melting point + 50 ° C.
- kneading method 1) A method in which liquid crystalline polyester, fillers and other additives are added in a lump from the original feeder and kneaded (collective kneading method) 2) A liquid crystalline polyester and other additives are preincorporated A method in which a filler and other additives are added and kneaded from a side feeder after being fed from a feeder and kneaded (side feed method), 3) high concentration of liquid crystalline polyester and other additives Any method may be used such as a method of preparing a liquid crystalline polyester composition (master pellet) containing the master pellet and then kneading the master pellet with liquid crystalline polyester and a filler (master pellet method) so as to obtain a prescribed concentration. .
- the liquid crystalline polyester resin composition of the embodiment of the present invention has an excellent surface appearance by performing known melt molding such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc. Color) and mechanical properties, heat resistance and flame retardancy.
- the molded product include injection molded products, extrusion molded products, press molded products, sheets, pipes, unstretched films, uniaxially stretched films, various films such as biaxially stretched films, unstretched yarns, superstretched yarns, and the like. Examples include various fibers. In particular, the effect of the present invention can be remarkably obtained when injection molding is used.
- Molded articles made of liquid crystalline polyester or liquid crystalline polyester resin composition thus obtained include, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, relay bases, and relays. Spool, switch, coil bobbin, condenser, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, housing, Electrical / electronic parts such as semiconductors, liquid crystal display parts, FDD carriages, FDD chassis, HDD parts, motor brush holders, parabolic antennas, computer-related parts, VTR parts, TV parts, Ron, hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disks / compact disks, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc.
- composition analysis and characteristic evaluation of the liquid crystalline polyester were performed by the following methods.
- 1 H-NMR 1 H-nuclear magnetic resonance spectrum
- GPC GPC device: Made by Waters Detector: Differential refractive index detector RI2410 (manufactured by Waters) Column: Shodex K-806M (two), K-802 (one) (Showa Denko) Eluent: pentafluorophenol / chloroform (35/65 w / w%) Measurement temperature: 23 ° C Flow rate: 0.8mL / min Sample injection amount: 200 ⁇ L (concentration: 0.1%) (LALLS) Apparatus: Low-angle laser light scattering photometer KMX-6 (manufactured by Chromatix) Detector wavelength: 633 nm (He-Ne) Detector temperature: 23 ° C
- liquid crystalline polyesters 12 types of liquid crystalline polyesters (a-1) to (a-6), (b-1) to (b-5) and (b-1 ′) were prepared as Production Examples 1 to 12. Produced. And about each produced liquid crystalline polyester, the composition analysis mentioned above, the measurement of melting
- the temperature was increased at a temperature rate of 0.68 ° C./min, and the temperature was increased from 270 ° C. to 350 ° C. at an average temperature increase rate of 1.4 ° C./min.
- the temperature raising time was 4 hours.
- the polymerization temperature was maintained at 350 ° C.
- the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour
- the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg ⁇ cm.
- the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- a liquid crystalline polyester (a-1) was obtained.
- composition analysis of the liquid crystalline polyester (a-1) was conducted.
- structural unit derived from p-hydroxybenzoic acid (structural unit (I)) relative to the total of the structural unit derived from hydroquinone (structural unit (III)) was 75 mol%.
- structural unit (II) 4,4'-dihydroxybiphenyl-derived structural unit
- structural unit (III) hydroquinone-derived structural unit
- structural unit (IV) terephthalic acid-derived structural unit
- isophthalic acid The sum of the structural units derived from the acid (structural unit (V)) was substantially equimolar. Further, Tm was 330 ° C., ⁇ S was 2.2 ⁇ 10 ⁇ 3 J / g ⁇ K, the number average molecular weight was 11,800, the degree of dispersion was 1.8, and the melt viscosity was 28 Pa ⁇ s.
- the temperature was increased at a temperature rate of 0.63 ° C./min, and the temperature was increased from 270 ° C. to 335 ° C. at an average temperature increase rate of 1.6 ° C./min.
- the temperature raising time was 4 hours.
- the polymerization temperature was maintained at 335 ° C.
- the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour
- the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg ⁇ cm.
- the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- a liquid crystalline polyester (a-2) was obtained.
- the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 73 mol%. there were.
- the ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 65 mol%.
- the ratio of structural unit (IV) to the total of structural unit (IV) and structural unit (V) was 85 mol%.
- the total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm was 317 ° C.
- ⁇ S was 1.5 ⁇ 10 ⁇ 3 J / g ⁇ K
- the number average molecular weight was 10,900
- the degree of dispersion was 2.0
- the melt viscosity was 23 Pa ⁇ s.
- the temperature was increased at a temperature rate of 0.72 ° C./min, and the temperature was increased from 270 ° C. to 350 ° C. at an average temperature increase rate of 1.2 ° C./min.
- the temperature raising time was 4 hours.
- the polymerization temperature was maintained at 350 ° C.
- the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour
- the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg ⁇ cm.
- the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- a liquid crystalline polyester (a-3) was obtained.
- the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 78 mol%. there were.
- the ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 70 mol%.
- the ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 70 mol%.
- the total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm was 338 ° C.
- ⁇ S was 2.6 ⁇ 10 ⁇ 3 J / g ⁇ K
- the number average molecular weight was 13,200
- the degree of dispersion was 2.2
- the melt viscosity was 40 Pa ⁇ s.
- the temperature was increased at a temperature rate of 0.64 ° C./min, and the temperature was increased from 270 ° C. to 330 ° C. at an average temperature increase rate of 1.3 ° C./min.
- the temperature raising time was 4 hours.
- the polymerization temperature was maintained at 330 ° C.
- the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour
- the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg ⁇ cm.
- the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- a liquid crystalline polyester (a-4) was obtained.
- the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 70 mol%. there were.
- the ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 58 mol%.
- the ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 65 mol%.
- the total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm was 310 ° C.
- ⁇ S was 1.2 ⁇ 10 ⁇ 3 J / g ⁇ K
- the number average molecular weight was 12,000
- the degree of dispersion was 2.1
- the melt viscosity was 30 Pa ⁇ s.
- the temperature was increased at a temperature rate of 0.67 ° C./min, and the temperature was increased from 270 ° C. to 330 ° C. at an average temperature increase rate of 1.1 ° C./min.
- the temperature raising time was 4 hours.
- the polymerization temperature was maintained at 330 ° C.
- the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour
- the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg ⁇ cm.
- the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- a liquid crystalline polyester (a-5) was obtained.
- the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 68 mol%. there were.
- the ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 75 mol%.
- the ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 85 mol%.
- the total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm was 309 ° C.
- ⁇ S was 1.1 ⁇ 10 ⁇ 3 J / g ⁇ K
- the number average molecular weight was 11,300
- the degree of dispersion was 2.3
- the melt viscosity was 26 Pa ⁇ s.
- the temperature was increased at a temperature rate of 0.81 ° C./min, and the temperature was increased from 270 ° C. to 355 ° C. at an average temperature increase rate of 1.0 ° C./min.
- the temperature raising time was 4 hours.
- the polymerization temperature was maintained at 355 ° C.
- the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour
- the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg ⁇ cm.
- the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- a liquid crystalline polyester (a-6) was obtained.
- Composition analysis of the liquid crystalline polyester (a-6) revealed that the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 80 mol%. there were.
- the ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 55 mol%.
- the ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 60 mol%.
- the total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm was 344 ° C.
- ⁇ S was 2.7 ⁇ 10 ⁇ 3 J / g ⁇ K
- the number average molecular weight was 12,700
- the degree of dispersion was 2.5
- the melt viscosity was 35 Pa ⁇ s.
- the temperature was increased at a temperature rate of 0.68 ° C./min, and the temperature was increased from 270 ° C. to 320 ° C. at an average temperature increase rate of 0.9 ° C./min.
- the temperature raising time was 4 hours.
- the polymerization temperature was maintained at 320 ° C.
- the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour
- the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg ⁇ cm.
- the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- a liquid crystalline polyester (b-1) was obtained.
- Composition analysis of the liquid crystalline polyester (b-1) revealed that the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 65 mol%. there were.
- the ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 60 mol%.
- the ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 55 mol%.
- the total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm was 303 ° C.
- ⁇ S was 0.8 ⁇ 10 ⁇ 3 J / g ⁇ K
- the number average molecular weight was 13,500
- the degree of dispersion was 2.7
- the melt viscosity was 43 Pa ⁇ s.
- the temperature was increased at a temperature rate of 0.71 ° C./min, and the temperature was increased from 270 ° C. to 365 ° C. at an average temperature increase rate of 1.5 ° C./min.
- the temperature raising time was 4 hours.
- the polymerization temperature was maintained at 365 ° C.
- the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour
- the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg ⁇ cm.
- the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- a liquid crystalline polyester (b-2) was obtained.
- Composition analysis of the liquid crystalline polyester (b-2) revealed that the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 85 mol%. there were.
- the ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 60 mol%.
- the ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 90 mol%.
- the total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm was 351 ° C.
- ⁇ S was 3.2 ⁇ 10 ⁇ 3 J / g ⁇ K
- the number average molecular weight was 12,200
- the degree of dispersion was 2.6
- the melt viscosity was 31 Pa ⁇ s.
- Composition analysis of the liquid crystalline polyester (b-3) revealed that the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 75 mol%. there were.
- the ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 60 mol%.
- the ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 76 mol%.
- the total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm was 331 ° C.
- ⁇ S was 0.9 ⁇ 10 ⁇ 3 J / g ⁇ K
- the number average molecular weight was 12,100
- the degree of dispersion was 2.6
- the melt viscosity was 31 Pa ⁇ s.
- the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 75 mol%. there were.
- the ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 60 mol%.
- the ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 76 mol%.
- the total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm was 330 ° C.
- ⁇ S was 3.1 ⁇ 10 ⁇ 3 J / g ⁇ K
- the number average molecular weight was 12,000
- the degree of dispersion was 2.6
- the melt viscosity was 30 Pa ⁇ s.
- the temperature was raised at °C / min, and the temperature was raised from 270 ° C to 335 ° C at an average rate of temperature rise of 1.5 ° C / min.
- the temperature raising time was 4 hours.
- the polymerization temperature was maintained at 335 ° C.
- the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour
- the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg ⁇ cm.
- the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- a liquid crystalline polyester (b-5) was obtained.
- composition analysis of this liquid crystalline polyester (b-5) revealed that the structural unit (I) was 66.7 mol%, the structural unit (II) was 6.3 mol%, and the ethylenedioxy unit derived from polyethylene terephthalate was The content was 10.4 mol% and the structural unit (IV) was 16.6 mol%. Further, Tm was 313 ° C., ⁇ S was 1.9 ⁇ 10 ⁇ 3 J / g ⁇ K, the number average molecular weight was 9,800, the degree of dispersion was 2.8, and the melt viscosity was 13 Pa ⁇ s.
- the oil agent which consists of the water emulsion of the emulsifier made was given, and all the filaments were taken up by the 1st godet roll. After passing this through the second godet roll at the same speed, one of all the filaments is sucked with a suction gun, and the remaining one is passed through a dancer arm through a pirn winder (EFT take-up winder manufactured by Kozu Seisakusho, It was wound up in the shape of a pan with no contact roll in contact with the winding package.
- EFT take-up winder manufactured by Kozu Seisakusho
- Composition analysis of the liquid crystalline polyester (b-1 ′) revealed that the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 65 mol%. Met. The ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 60 mol%. The ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 55 mol%. The total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar.
- Tm3 endothermic peak temperature
- Tm3 endothermic peak temperature
- Examples 1 to 6, Comparative Examples 1 to 5 The pellets of liquid crystalline polyester (a-1 to a-6, b-1 to b-5) obtained in each production example were dried with hot air. The liquid crystalline polyesters (a-1) to (a-6) after hot air drying were used as the liquid crystalline polyesters of Examples 1 to 6, respectively. The liquid crystalline polyesters (b-1) to (b-5) after hot air drying were used as the liquid crystalline polyesters of Comparative Examples 1 to 5, respectively. The following (1) to (3) were evaluated for the liquid crystalline polyesters of Examples 1 to 6 and Comparative Examples 1 to 5. The results are shown in Table 2.
- FIG. 1 is a conceptual diagram showing a measurement site for warpage. The length of the measured amount of warpage is shown as the amount of warpage 3 in FIG.
- the liquid crystalline polyester is supplied to a FANUC ⁇ 30C injection molding machine (FANUC screw diameter 28 mm), and a cylindrical molded product having a cylinder temperature of the melting point of the liquid crystalline polyester + 10 ° C., a height of 25 mm, ⁇ 1.5 mm, and a wall thickness of 0.15 mm is formed. did.
- the resulting molded product was subjected to a load with an orientec Tensilon UTR-1T lowered at a speed of 0.5 mm / min with a jig with a tip angle R of 0.5, and the primary peak pressure (N) was measured. The winding strength was evaluated.
- liquid crystalline polyester resin compositions of Examples 7 to 18 and the liquid crystalline polyester resin compositions of Comparative Examples 6 to 16 were produced. did.
- the filler used in each example and comparative example is shown below.
- C-1 E glass chopped strand (ECS-03T790DE) manufactured by Nippon Electric Glass
- C-2 Nippon Electric Glass glass milled fiber (EPDE-40M-10A)
- C-3 Mica manufactured by Yamaguchi Mica Industry (“Micalet” (registered trademark) 41PU5)
- C-4 Talc manufactured by Fuji Talc (NK64)
- Examples 7 to 18, Comparative Examples 6 to 16 Using a TEM35B type twin screw extruder manufactured by Toshiba Machine equipped with a side feeder, the liquid crystalline polyesters (a-1 to a-6, b-1 to b-5) obtained in each of the production examples are charged from the hopper and filled.
- the materials (c-1 to c-4) were added from the side in the blending amounts shown in Table 3 with respect to 100 parts by weight of the liquid crystalline polyester, the cylinder temperature was set to the melting point of the liquid crystalline polyester + 10 ° C., and melt kneading. It was set as a pellet.
- the pellets of the obtained liquid crystalline polyester resin composition were dried with hot air.
- liquid crystalline polyester resin compositions of Examples 7 to 18 and Comparative Examples 6 to 16 were obtained.
- the above evaluations (1) to (3) were performed.
- Table 3 shows the types of liquid crystalline polyesters and fillers, the content ratios, and the evaluation results in each Example and Comparative Example.
- liquid crystalline polyester resin compositions of Examples of the present invention have small variations in measurement time and injection peak pressure and are excellent in precision molding stability. Moreover, since it is excellent in dimensional stability at the time of reflow and has a high insulator winding strength, it can be seen that it is suitable for small precision molded products for electrical and electronic applications.
- the liquid crystalline polyester composition of the present invention is useful for small precision molded products such as connectors and insulators that require precision molding stability, dimensional stability during reflow, and strength as a small thin molded product.
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Abstract
Description
(Tmは示差熱量測定において、重合を完了したポリマーを室温から20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm1)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm2)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm3)を指し、ΔHmは該Tm3の吸熱ピーク面積(ΔHm3)である。)
本発明の実施形態としての液晶性ポリエステルは、溶融時に光学的異方性を示すサーモトロピック液晶ポリマーと呼ばれるポリエステルであり、下記構造単位(I)、(II)、(III)、(IV)および(V)から構成され、構造単位(I)は構造単位(I)、(II)および(III)の合計に対して68~80モル%であり、構造単位(II)は構造単位(II)および(III)の合計に対して55~75モル%であり、構造単位(IV)は構造単位(IV)および(V)の合計に対して60~85モル%であり、構造単位(II)および(III)の合計と(IV)および(V)の合計が実質的に等モルであり、下式[1]で定義されるΔS(融解エントロピー)が1.0~3.0×10-3J/g・Kであることを特徴とする。
(Tmは示差熱量測定において、重合を完了したポリマーを室温から20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm1)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm2)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm3)を指し、ΔHmは該Tm3の吸熱ピーク面積(ΔHm3)である。)
ΔS(J/g・K)=ΔHm(J/g)/Tm(K) [1]
ここでTm(融点)とは示差熱量測定において、重合を完了したポリマーを室温から20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm1)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm2)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm3)を指し、ΔHmは該Tm3の吸熱ピーク面積(ΔHm3)である。
本発明の実施形態の液晶性ポリエステルの数平均分子量は、3,000~50,000が好ましく、より好ましくは8,000~30,000、さらに好ましくは8,000~20,000の範囲である。
液晶性ポリエステルの組成分析および特性評価は以下の方法により行った。
液晶性ポリエステルの組成分析は、1H-核磁気共鳴スペクトル(1H-NMR)測定により実施した。液晶性ポリエステルをNMR試料管に50mg秤量し、溶媒(ペンタフルオロフェノール/1,1,2,2-テトラクロロエタン-d2=65/35(重量比)混合溶媒)800μLに溶解して、UNITY INOVA500型NMR装置(バリアン社製)を用いて観測周波数500MHz、温度80℃で1H-NMR測定を実施し、7~9.5ppm付近に観測される各構造単位由来のピーク面積比から組成を分析した。
示差走査熱量計DSC-7(パーキンエルマー製)により、室温から20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm1)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm2)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm3)を融点とし、融点とその吸熱ピーク面積(ΔHm3)から下式[1]によってΔS(J/g・K)を算出した。以下の製造例においては、融点をTm、融解エントロピーをΔSと記載する。
ΔS(J/g・K)=ΔHm(J/g)/Tm(K) [1]
液晶性ポリエステルの数平均分子量および重量平均分子量測定は、下記条件に示したゲル浸透クロマトグラフ(GPC)/LALLS法により測定した。また、重量平均分子量(Mw)を数平均分子量(Mn)で除して分散度(Mw/Mn)を算出した。
(GPC)
GPC装置:Waters製
検出器:示差屈折率検出器RI2410(Waters製)
カラム:Shodex K-806M(2本)、K-802(1本)(昭和電工製)
溶離液:ペンタフルオロフェノール/クロロホルム(35/65w/w%)
測定温度:23℃
流速:0.8mL/min
試料注入量:200μL (濃度:0.1%)
(LALLS)
装置:低角度レーザー光散乱光度計KMX-6(Chromatix製)
検出器波長:633nm(He-Ne)
検出器温度:23℃
高化式フローテスターCFT-500D(オリフィス0.5φ×10mm)(島津製作所製)を用い、温度は液晶性ポリエステルの融点+10℃、剪断速度は1000/秒で測定した。
撹拌翼、留出管を備えた5Lの反応容器にp-ヒドロキシ安息香酸932重量部、4,4’-ジヒドロキシビフェニル251重量部、ハイドロキノン99重量部、テレフタル酸284重量部、イソフタル酸90重量部および無水酢酸1252重量部(フェノール性水酸基合計の1.09当量)を仕込み、窒素ガス雰囲気下で撹拌しながら145℃で1時間反応させた後、ジャケット温度を145℃から270℃までを平均昇温速度0.68℃/分で昇温させ、270℃から350℃までを平均昇温速度1.4℃/分で昇温させた。昇温時間は4時間であった。その後、重合温度を350℃に保持し、1.0時間で1.0mmHg(133Pa)に減圧し、更に反応を続け、撹拌に要するトルクが20kg・cmに到達したところで重合を完了させた。次に反応容器内を1.0kg/cm2(0.1MPa)に加圧し、直径10mmの円形吐出口を1ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶性ポリエステル(a-1)を得た。
撹拌翼、留出管を備えた5Lの反応容器にp-ヒドロキシ安息香酸907重量部、4,4’-ジヒドロキシビフェニル294重量部、ハイドロキノン94重量部、テレフタル酸343重量部、イソフタル酸61重量部および無水酢酸1272重量部(フェノール性水酸基合計の1.09当量)を仕込み、窒素ガス雰囲気下で撹拌しながら145℃で1時間反応させた後、ジャケット温度を145℃から270℃までを平均昇温速度0.63℃/分で昇温させ、270℃から335℃までを平均昇温速度1.6℃/分で昇温させた。昇温時間は4時間であった。その後、重合温度を335℃に保持し、1.0時間で1.0mmHg(133Pa)に減圧し、更に反応を続け、撹拌に要するトルクが20kg・cmに到達したところで重合を完了させた。次に反応容器内を1.0kg/cm2(0.1MPa)に加圧し、直径10mmの円形吐出口を1ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶性ポリエステル(a-2)を得た。
撹拌翼、留出管を備えた5Lの反応容器にp-ヒドロキシ安息香酸970重量部、4,4’-ジヒドロキシビフェニル258重量部、ハイドロキノン65重量部、テレフタル酸230重量部、イソフタル酸99重量部および無水酢酸1222重量部(フェノール性水酸基合計の1.09当量)を仕込み、窒素ガス雰囲気下で撹拌しながら145℃で1時間反応させた後、ジャケット温度を145℃から270℃までを平均昇温速度0.72℃/分で昇温させ、270℃から350℃までを平均昇温速度1.2℃/分で昇温させた。昇温時間は4時間であった。その後、重合温度を350℃に保持し、1.0時間で1.0mmHg(133Pa)に減圧し、更に反応を続け、撹拌に要するトルクが20kg・cmに到達したところで重合を完了させた。次に反応容器内を1.0kg/cm2(0.1MPa)に加圧し、直径10mmの円形吐出口を1ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶性ポリエステル(a-3)を得た。
撹拌翼、留出管を備えた5Lの反応容器にp-ヒドロキシ安息香酸870重量部、4,4’-ジヒドロキシビフェニル292重量部、ハイドロキノン125重量部、テレフタル酸292重量部、イソフタル酸157重量部および無水酢酸1302重量部(フェノール性水酸基合計の1.09当量)を仕込み、窒素ガス雰囲気下で撹拌しながら145℃で1時間反応させた後、ジャケット温度を145℃から270℃までを平均昇温速度0.64℃/分で昇温させ、270℃から330℃までを平均昇温速度1.3℃/分で昇温させた。昇温時間は4時間であった。その後、重合温度を330℃に保持し、1.0時間で1.0mmHg(133Pa)に減圧し、更に反応を続け、撹拌に要するトルクが20kg・cmに到達したところで重合を完了させた。次に反応容器内を1.0kg/cm2(0.1MPa)に加圧し、直径10mmの円形吐出口を1ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶性ポリエステル(a-4)を得た。
撹拌翼、留出管を備えた5Lの反応容器にp-ヒドロキシ安息香酸845重量部、4,4’-ジヒドロキシビフェニル402重量部、ハイドロキノン79重量部、テレフタル酸407重量部、イソフタル酸72重量部および無水酢酸1322重量部(フェノール性水酸基合計の1.09当量)を仕込み、窒素ガス雰囲気下で撹拌しながら145℃で1時間反応させた後、ジャケット温度を145℃から270℃までを平均昇温速度0.67℃/分で昇温させ、270℃から330℃までを平均昇温速度1.1℃/分で昇温させた。昇温時間は4時間であった。その後、重合温度を330℃に保持し、1.0時間で1.0mmHg(133Pa)に減圧し、更に反応を続け、撹拌に要するトルクが20kg・cmに到達したところで重合を完了させた。次に反応容器内を1.0kg/cm2(0.1MPa)に加圧し、直径10mmの円形吐出口を1ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶性ポリエステル(a-5)を得た。
撹拌翼、留出管を備えた5Lの反応容器にp-ヒドロキシ安息香酸994重量部、4,4’-ジヒドロキシビフェニル184重量部、ハイドロキノン89重量部、テレフタル酸179重量部、イソフタル酸120重量部および無水酢酸1202重量部(フェノール性水酸基合計の1.09当量)を仕込み、窒素ガス雰囲気下で撹拌しながら145℃で1時間反応させた後、ジャケット温度を145℃から270℃までを平均昇温速度0.81℃/分で昇温させ、270℃から355℃までを平均昇温速度1.0℃/分で昇温させた。昇温時間は4時間であった。その後、重合温度を355℃に保持し、1.0時間で1.0mmHg(133Pa)に減圧し、更に反応を続け、撹拌に要するトルクが20kg・cmに到達したところで重合を完了させた。次に反応容器内を1.0kg/cm2(0.1MPa)に加圧し、直径10mmの円形吐出口を1ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶性ポリエステル(a-6)を得た。
撹拌翼、留出管を備えた5Lの反応容器にp-ヒドロキシ安息香酸808重量部、4,4’-ジヒドロキシビフェニル352重量部、ハイドロキノン139重量部、テレフタル酸288重量部、イソフタル酸235重量部および無水酢酸1352重量部(フェノール性水酸基合計の1.09当量)を仕込み、窒素ガス雰囲気下で撹拌しながら145℃で1時間反応させた後、ジャケット温度を145℃から270℃までを平均昇温速度0.68℃/分で昇温させ、270℃から320℃までを平均昇温速度0.9℃/分で昇温させた。昇温時間は4時間であった。その後、重合温度を320℃に保持し、1.0時間で1.0mmHg(133Pa)に減圧し、更に反応を続け、撹拌に要するトルクが20kg・cmに到達したところで重合を完了させた。次に反応容器内を1.0kg/cm2(0.1MPa)に加圧し、直径10mmの円形吐出口を1ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶性ポリエステル(b-1)を得た。
撹拌翼、留出管を備えた5Lの反応容器にp-ヒドロキシ安息香酸1057重量部、4,4’-ジヒドロキシビフェニル151重量部、ハイドロキノン59重量部、テレフタル酸202重量部、イソフタル酸22重量部および無水酢酸1152重量部(フェノール性水酸基合計の1.09当量)を仕込み、窒素ガス雰囲気下で撹拌しながら145℃で1時間反応させた後、ジャケット温度を145℃から270℃までを平均昇温速度0.71℃/分で昇温させ、270℃から365℃までを平均昇温速度1.5℃/分で昇温させた。昇温時間は4時間であった。その後、重合温度を365℃に保持し、1.0時間で1.0mmHg(133Pa)に減圧し、更に反応を続け、撹拌に要するトルクが20kg・cmに到達したところで重合を完了させた。次に反応容器内を1.0kg/cm2(0.1MPa)に加圧し、直径10mmの円形吐出口を1ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶性ポリエステル(b-2)を得た。
145℃から270℃までの平均昇温速度を0.83℃/分、270℃から350℃までの平均昇温速度を0.9℃/分に変更した以外は製造例1と同様に重合を行い、液晶性ポリエステル(b-3)を得た。
145℃から270℃までの平均昇温速度を0.65℃/分、270℃から350℃までの平均昇温速度を1.7℃/分に変更した以外は製造例1と同様に重合を行い、液晶性ポリエステル(b-4)を得た。
撹拌翼、留出管を備えた5Lの反応容器にp-ヒドロキシ安息香酸995重量部、4,4’-ジヒドロキシビフェニル126重量部、テレフタル酸112重量部、ポリエチレンテレフタレート216重量部および無水酢酸969重量部(フェノール性水酸基合計の1.09当量)を仕込み、窒素ガス雰囲気下で撹拌しながら130℃で2時間反応させた後、ジャケット温度を145℃から270℃までを平均昇温速度0.64℃/分で昇温させ、270℃から335℃までを平均昇温速度1.5℃/分で昇温させた。昇温時間は4時間であった。その後、重合温度を335℃に保持し、1.0時間で1.0mmHg(133Pa)に減圧し、更に反応を続け、撹拌に要するトルクが20kg・cmに到達したところで重合を完了させた。次に反応容器内を1.0kg/cm2(0.1MPa)に加圧し、直径10mmの円形吐出口を1ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶性ポリエステル(b-5)を得た。
製造例7の液晶性ポリエステル(b-1)を用い、160℃、12時間の真空乾燥を行った後、大阪精機工作株式会社製φ15mm単軸エクストルーダーにて溶融押し出しし、ギアーポンプで計量しつつ紡糸パックにポリマーを供給した。紡糸パックでは金属不織布フィルターを用いてポリマーを濾過し、口金よりポリマーを吐出した。吐出したポリマーは40mmの保温領域を通過させた後、25℃、空気流の環状冷却風により糸条の外側から冷却し固化させ、その後、ポリエーテル化合物を主体とする平滑剤とラウリルアルコールを主体とする乳化剤の水エマルジョンからなる油剤を付与し全フィラメントを第1ゴデットロールに引き取った。これを同じ速度である第2ゴデットロールを介した後、全フィラメント中の1本以外はサクションガンにて吸引し、残り1本はダンサーアームを介しパーンワインダー(神津製作所社製EFT型テークアップワインダー、巻取パッケージに接触するコンタクトロール無し)にてパーンの形状に巻き取った。
各製造例で得られた液晶性ポリエステル(a-1~a-6、b-1~b-5)のペレットを熱風乾燥した。熱風乾燥後の液晶性ポリエステル(a-1)~(a-6)を、それぞれ、実施例1~6の液晶性ポリエステルとした。また、熱風乾燥後の液晶性ポリエステル(b-1)~(b-5)を、それぞれ、比較例1~5の液晶性ポリエステルとした。実施例1~6および比較例1~5の液晶性ポリエステルについて、以下に示す(1)~(3)の評価を行った。結果は表2に示す。
液晶性ポリエステルをファナックα30C射出成形機(ファナック製スクリュー径28mm)に供し、シリンダー温度を液晶性ポリエステルの融点+10℃、スクリュー回転数を150rpm、背圧を2.0MPaとして8mm計量した際の計量時間、および0.3mmピッチ70芯ファインピッチコネクター(壁厚0.2mm)金型での成形時のピーク圧力を求めた。これを500ショット行い、計量時間とピーク圧の標準偏差を算出し、精密成形安定性を評価した。
上記(1)記載の方法により得られたファインピッチコネクターを、リフローシミュレーターcore9030c(株式会社コアーズ製)により、1.6℃/秒で200℃まで昇温して2分間プリヒートし、表面最高温度260℃で30秒間リフローさせた後に室温まで冷却させてリフロー処理を行った。リフロー処理前後のそり量をそれぞれ測定し、リフロー後そり量をリフロー前そり量で除して100分率とし、リフロー時の寸法変化を評価した。なおそり量は、ファインピッチコネクターの長尺方向を水平な定盤の上に静置して、万能投影機(V-16A(Nikon製))を用いて、ファインピッチコネクター底面の水平定盤に対する最大変位量とした。図1は、そり量の測定部位を示す概念図である。測定したそり量の長さを、図1ではそり量3として示す。
液晶性ポリエステルをファナックα30C射出成形機(ファナック製スクリュー径28mm)に供し、シリンダー温度を液晶性ポリエステルの融点+10℃で高さ25mm、φ1.5mm、壁厚0.15mmの円筒状成形品を成形した。得られた成形品について、オリエンテック製テンシロンUTR-1Tにより先端角度R:0.5の治具を速度0.5mm/分で降下させて荷重を掛け、その一次ピーク圧(N)を測定し、巻き線強度を評価した。
(c-1):日本電気硝子製Eガラスチョップドストランド(ECS-03T790DE)
(c-2):日本電気硝子製ガラスミルドファイバー(EPDE-40M-10A)
(c-3):山口雲母工業製造粒マイカ(“ミカレット”(登録商標)41PU5)
(c-4):富士タルク工業製タルク(NK64)
サイドフィーダーを備えた東芝機械製TEM35B型2軸押出機で、各製造例で得られた液晶性ポリエステル(a-1~a-6、b-1~b-5)をホッパーから投入し、充填材(c-1~c-4)を液晶性ポリエステル100重量部に対して表3に示す配合量でサイドから投入し、シリンダー温度を液晶性ポリエステルの融点+10℃に設定し、溶融混練してペレットとした。得られた液晶性ポリエステル樹脂組成物のペレットを熱風乾燥した。これにより、実施例7~18および比較例6~16の液晶性ポリエステル樹脂組成物を得た。得られた実施例7~18および比較例6~16の液晶性ポリエステル樹脂組成物について、上記(1)~(3)の評価を行った。なお、(1)精密成形安定性評価では背圧を、1.5MPaとし、(3)インシュレーター巻き線強度評価では、シリンダー温度を液晶性ポリエステルの融点+10℃で高さ25mm、φ1.2mm、壁厚0.3mmの円筒状成形品を成形した。各実施例および比較例における液晶性ポリエステルおよび充填材の種類、これらの含有割合、および評価結果を、表3に示す。
2.コネクター長尺方向
3.そり量
Claims (5)
- 下記構造単位(I)、(II)、(III)、(IV)および(V)から構成され、構造単位(I)は構造単位(I)、(II)および(III)の合計に対して68~80モル%であり、構造単位(II)は構造単位(II)および(III)の合計に対して55~75モル%であり、構造単位(IV)は構造単位(IV)および(V)の合計に対して60~85モル%であり、構造単位(II)および(III)の合計と(IV)および(V)の合計が実質的に等モルであり、下式[1]で定義されるΔS(融解エントロピー)が1.0~3.0×10-3J/g・Kであることを特徴とする液晶性ポリエステル。
(Tmは、液晶性ポリエステルの示差熱量測定において、室温から20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm1)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm2)の観測後、Tm1+20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却し、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm3)を指し、ΔHmは該Tm3の吸熱ピーク面積(ΔHm3)である。) - 重量平均分子量(Mw)を数平均分子量(Mn)で除した分散度(Mw/Mn)が2.5以下である請求項1記載の液晶性ポリエステル。
- 液晶性ポリエステルの原料である芳香族ヒドロキシカルボン酸および芳香族ジオールの水酸基を、無水酢酸を用いてアセチル化した後、脱酢酸重合することにより液晶性ポリエステルを製造する方法であって、脱酢酸重合時のジャケット温度を、270℃から重合最高温度までの平均昇温速度が1.0~1.6℃/分となるように昇温することを特徴とする請求項1または2に記載の液晶性ポリエステルの製造方法。
- 請求項1または2に記載の液晶性ポリエステル100重量部に対して、充填材を10~200重量部含有することを特徴とする液晶性ポリエステル樹脂組成物。
- 請求項1または2に記載の液晶性ポリエステルまたは請求項4に記載の液晶性ポリエステル樹脂組成物を溶融成形してなる成形品。
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Cited By (3)
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JP2013108191A (ja) * | 2011-11-21 | 2013-06-06 | Sumitomo Chemical Co Ltd | 繊維製造用材料および繊維 |
JP2016014217A (ja) * | 2015-10-19 | 2016-01-28 | 住友化学株式会社 | 繊維製造用材料および繊維 |
WO2023199854A1 (ja) * | 2022-04-11 | 2023-10-19 | 東レ株式会社 | 液晶ポリエステル樹脂、液晶ポリエステル樹脂組成物およびそれからなる成形品 |
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JP5437514B1 (ja) * | 2013-04-09 | 2014-03-12 | 鉦則 藤田 | 複合形成材料、射出成形品及び複合形成材料の製造方法 |
CN105358657A (zh) | 2013-06-07 | 2016-02-24 | 提克纳有限责任公司 | 高强度热致液晶聚合物 |
US20230065239A1 (en) * | 2020-01-17 | 2023-03-02 | Toray Industries, Inc. | Liquid crystal polyester resin, liquid crystal polyester resin composition, formed product, layered body and liquid crystal polyester resin film, and production method therefor |
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- 2011-12-14 KR KR1020137015744A patent/KR101313501B1/ko active IP Right Grant
- 2011-12-14 WO PCT/JP2011/006969 patent/WO2012090406A1/ja active Application Filing
- 2011-12-14 JP JP2012506028A patent/JP5126453B2/ja active Active
- 2011-12-14 CN CN201180062650.3A patent/CN103282404B/zh active Active
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Publication number | Publication date |
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KR20130082513A (ko) | 2013-07-19 |
KR101313501B1 (ko) | 2013-10-01 |
TWI432516B (zh) | 2014-04-01 |
EP2660265A4 (en) | 2017-04-19 |
US9109159B2 (en) | 2015-08-18 |
EP2660265A1 (en) | 2013-11-06 |
CN103282404A (zh) | 2013-09-04 |
CN103282404B (zh) | 2015-01-21 |
TW201231551A (en) | 2012-08-01 |
EP2660265B1 (en) | 2019-09-04 |
JP5126453B2 (ja) | 2013-01-23 |
US20130270481A1 (en) | 2013-10-17 |
JPWO2012090406A1 (ja) | 2014-06-05 |
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